....CHDE....FRGB..ITLI............................MDIM360 - Ver 2.5 (21 Aug 1997) 2100000/00041040EUROPEAN PATENT SPECIFICATIONB119850109EP81810171.919810506enenen3601/8019800508CH3602/8019800508CH3603/8019800508CH3604/8019800508CH3605/8019800508CH3606/8019800508CH3735/8019800513CH3736/8019800513CH3737/8019800513CH4183/8019800529CH4184/8019800529CH4185/8019800529CH5079/8019800701CH5080/8019800701CH5081/8019800701CH9104/8019801210CH9105/8019801210CH9106/8019801210CH198501091985021981120219814819850109198502198402294 4C 09B 44/00 A 4C 09B 45/00 B 4D 06P 3/32 B 4D 21H 1/46 BdeSulphogruppenfreie basische Azoverbindungen in Metallkomplexform, in metallfreier Form und Verfahren zur Herstellung der VerbindungenenSulphofree basic azo compounds in metal complex form, in metal-free form and method for preparing the samefrComposés azoiques basiques exempts de groupes sulfo sous forme de complexes métallifères, complexes exempts de métal et procédé pour la préparation de ces composés83100106.000938281983010783100107.8009382919830107SANDOZ AG00201941150-4424Lichtstrasse 354002 BaselCHDoswald, PaulEschenstrasse 4CH-4142 MünchensteinCHMoriconi, EmilPasswangstrasse 59CH-4059 BasleCHMoser, HelmutLibellenstrasse 25CH-4104 OberwilCHSchmid, HorstHabshagstrasse 13CH-4153 ReinachCHCHDEFRGBITLI19811202198148

The invention relates to sulpho-free basic azo compounds, in 1:1 metal complex or 1:2 metal complex form, which are useful for dyeing paper and leather, to these compounds in metal-free form, and to a method to prepare the same.

What is meant by a "1:1 metal complex" is that each molecule of the complex has 1 metal atom bonded to 1 dyestuff molecule or has 2 metal atoms bonded to two dyestuff units, which dyestuff units are joined together by a direct bond or a conventional bridging group; and what is meant by a "1:2 metal complex" is that the complex has 1 atom of metal bonded to two dyestuff units, which dyestuff units can be the same or different but which dyestuff units are part of two separate dyestuff molecules.

The invention provides sulpho-free azo compounds, in 1:1 metal complex or 1:2 metal complex form or in metal-free form having on average at leat 1.3 preferably 2, water solubilising basic groups, the compounds being of the formula II where


with the proviso that

Preferably when the compounds of the invention are in 1:1 metal complex form Me is copper, chromium, cobalt, iron, nickel or manganese, more preferably copper, chromium or cobalt, most preferably copper. Preferably copper is Cu2+; chromium is Cr2+; cobalt is Co2+; iron is Fe2+; nickel is Ni2+ and manganese is Mn2+.

Preferably when the compounds of the invention are in 1:2 metal complex form, Me is chromium, cobalt. iron or nickel, more preferably chromium, cobalt or iron, most preferably iron. Preferably chromium is Cr3+; cobalt is Co3+, iron is Fe3+ and nickel is Ni3+.

Preferably the compounds of the invention when in 1:2 metal complex form and/or in metal free form when n = 2, are symmetric, i.e. both dyestuff molecules bonded to the metal ion are the same.

A group of preferred azo compounds of formula II' in metal-free form are those of formula Ila in which A1 is -OH or NH2, or where each R2a independently is hydrogen, each R3a, independently is hydrogen, in which


and all the other symbols are as defined above.

A further group of preferred metal-free azo compounds of formula II' are those of formula IIb in which is or where

Preferred compounds of formula IIb are of the formula Ilc in which

Preferred azo compounds of formula II' when in 1:1 metal complex form and when c =1 are of the formula lid in which Z2―D1, , A2, R2a and R3a are defined above and is ―NH― or ―O― with the proviso that in ring B each azo bridge to the ring C is ortho to A; and Mea is copper, cobalt, iron or chromium.

Preferred compounds of the formula Ild are of the formula Ile in which is hydrogen,


all the other symbols are as defined above.

Alternatively preferred compounds of formula II' in 1:1 metal complex form where c = 2 are of the formula Ilf in which the symbols are above defined and the group Xa is attached to each ring C in the meta- or para-position with respect to the azo bridge and the rings C carry no further substituents.

Preferred compounds of formula IIf are of the formula IIg in which the symbols are as above defined, and with the proviso that Xb is in a meta- or para-position to the azo bridge.

A further group of preferred compounds of formula II' in 1:1 metal complex form are of formula Ilh in which

More preferred compounds of formula IIh are of the formula IIi in which

Preferred 1:2 metal complex azo compounds of formula II' where c is 1 and are one of the formulae IIj to IIm below: in which


and the other symbols are as defined above.

Preferred compounds of formula IIj are symmetric and are of the formula IIn in which

The azo compounds of the invention in metal-free form may be prepared by coupling a diazotised amine of formula y with a coupling component of the formula where

The azo compounds of formula II' in 1:1 metal complex form may be prepared by metallising compounds of formula II' in metal-free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium or zinc.

The azo compounds of formula II' in 1:2 metal complex form may be prepared by metallising compounds of formula 11' in metal free form with a metal selected from chromium, nickel, cobalt or iron.

A further method for the preparation of an azo compound of formula II' in 1:2 metal complex form is bonding an azo compound of formula II' in metal free form with an azo compound 1:1 metal complex form when the metal is chromium, nickel, cobalt or iron.

The metallisation process to form a 1:1 metal complex is advantageously carried out by treating 1 mole of azo compounds with a metallising agent containing 1 equivalent of metal.

Metallisation is carried out by known methods advantageously in aqueous medium or a mixture of water and a water-miscible organic solvent for example acetone, lower alkyl alcohols, dimethylformamide, formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7. The metallisation process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.

Alternatively metallisation may be effected in a wholly organic medium (for example dimethylformamide). Advantageously for instance cobaltisation may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio of 2 to 6 moles of nitrite per gram atom of cobalt.

Suitable cobalt-yielding compounds are for example cobalt (II) or Co (III) sulphate, acetate, formate or chloride.

Copper-yielding compounds are for example cupric sulphate, cupric formate, cupric acetate or cupric chloride.

The nickel-yielding compounds are Ni (II) or Ni (III) compounds, such as nickel formate, nickel acetate or nickel sulphate.

Preferred manganese yielding compounds are Mn (II) compounds and iron yielding compounds are Fe (II) or Fe (111) compounds. Examples of these and zinc-yielding compounds are manganese-, iron-or zinc formate, acetate or sulphate.

Preferred chromium yielding compounds are Cr (II) or Cr (III) formate, acetate or sulphate.

The starting compounds of formula y and 8 are for the most part known or can be prepared according to known methods.

The coupling can be carried out according to known methods. Advantageously coupling is carried out in aqueous, acid, neutral or alkali medium at a temperature from -10°C to room temperature, if necessary in the presence of a coupling accelerator such as pyridine or urea. Alternatively, coupling may be effected in a mixture of solvents for example water and an organic solvent.

In the compounds of the invention the anion A° can be any non-chromophoric anion conventional in basic dyestuff chemistry. Suitable anions include such as chloride and bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzosulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate, as well as complex anions for example zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or of addition products of orthoboric acid with polyalcohols with at least an cis diol group present. These anions can be exchanged for each other by ion exchange resins or by reaction with acids or salts (for example via the hydroxide or bicarbonate or according to DE-A-2 001 748 or 2 001 816).

The compounds according to the invention are suitably worked up into a solid or liquid preparation for example by granulation or by dissolving in a suitable solvent. The compounds of the invention are suitable for dyeing, padding or printing on fibres, threads or textile materials particularly natural or regenerated cellulose materials for example cotton, synthetic polyamides or synthetic polyesters in which the acid groups have been modified. Such polyamide is described in BE-A-706,104 and such synthetic polyester is described in US-A-3 379 723.

The new compounds are also used for dyeing, pad-dyeing or printing fibres, threads or textiles produced therefrom, which consist of or contain homo- or mixed polymers of acrylonitrile or of asymmetrical dicyanoethylene.

The textile material is dyed, printed or pad-dyed in accordance with known methods. Acid modified-polyamide is dyed particularly advantageously in an aqueous, neutral or acid medium, at temperatures of 60°C to boiling point or at temperatures of above 100°C under pressure.

The textile material may also be dyed by the compounds of formula II' in organic solvents, e.g. in accordance with the directions given in DE-A-2 437 549.

Cellulose material is mainly dyed by the exhaust process, e.g. from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1 :1 to 1:100, and preferably from 1 :20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1:5 to 1:15, and the pH value of the dye baths varies between 3 and 10. Dyeing preferably takes place in the presence of electrolytes.

Printing may be effected by impregnation with a printing paste produced by known methods.

The dyestuffs are also suitable for dyeing or printing paper, e.g. for the production of bulk-dyed, sized and unsized paper. The dyestuffs may similarly be used for dyeing paper by the dipping process. The dyeing of paper is effected by known methods.

The new dyestuffs are also suitable for dyeing or printing leather by known methods. Dyeings with good fastness are obtained both on paper and on leather.

Dyeings made from the new compounds on leather have good light fastness properties, good diffusion properties with PVC, good water-, wash- and sweat properties, good fastness to dry cleaning, good fastness to drops of water, good fastness to hard water.

Dyeings made from the new compounds on paper have good build-up, good light fastness, good fastness to water, milk, fruit juice, sweetened mineral water and alcoholic drinks, good fastness to 1% sodium chloride, washing powder solution, good sulphite reductive or oxidative (with hypochlorite) clearance and good fastness to hard water. Dyeings made from mixtures of the new dyestuffs remain tone-in-tone and the nuance stability of dyeings made from the dyestuffs is good.

Further the dyestuffs of the invention do not run after dyeing on paper nor on the whole are they pH sensitive.

The new compounds may be converted into dyeing preparations. The processing into stable, liquid or solid dyeing preparations may take place in a generally known manner. Advantageously by grinding or granulating, or by dissolving in suitable solvents, optionally adding an assistant, e.g. a stabiliser or dissolving intermediary, such as urea. Such preparations may be obtained for example as described in FR-A-1.572.030 and 1.581.900 or in accordance with DE-A-2.001.748 and 2.001.816.

Liquid preparations or the compounds of formula II' preferably comprise 10-30% by weight of a compound of formula II' and to 30% of a solubilising agent such as urea, lactic acid or acetic acid the rest of the composition being water. Solid preparations preferably comprising 20-80% dyestuff, 80-20% solubilising agent such as urea or Na2S04 and 2-5% water.

In the following examples all parts and percentages given are by weight and the temperatures given are in degrees centrigrade unless indicated to the contrary.

Example 1

a) 15.4 Parts (1/10 mole of 1-hydroxy-2-amino-4-nitrobenzol are coupled with 11 parts of resorcinol to give a compound of the formula Via

b) 24 Parts (1/10 mole) of 2(4'-aminophenyl)-6-methylbenzthiazole was chloromethylated according to the method of DE-A-1 965 993 and then quaternised with 50 parts of a solution of trimethylamine in water at 40-45°. The resulting trimethylammonium compound is dissolved at 0-10° in dilute hydrochloric acid solution and is diazotised with 6.9 parts of sodium nitrite and the dyestuff suspension of the compound of formula Via is dropwise added. A compound of the formula Vlb

c) 15.4 Parts (1/10 mole) of the dyestuff of formula b) is dissolved in 500 parts formamide. The solution is warmed to 60° to give a solution of 35 parts sodium acetate and 35 parts of KCr(S041z 12H20 is added and the temperature is raised to 90-950. After about 60 minutes metallisation is ended. The reaction mixture is cooled to 20° and is precipitated in acetone to give a 1:2 chromium complex of the formula Vlc

In the following Examples

Examples 2 to 11

The following Examples are compounds of the formula or in 1:1 metal complex or 1:2 metal complex form. These compounds can be prepared according to the method of Example 1 with suitable choice of starting materials. Each Z referred to in a specific Example has the same significance in that Example whenever it appears.

Examples 11-37

The following Examples are of compounds of the formula and in 1:1 metal complex and 1:2 metal complex form and may be prepared according to the method of Example 1.

The dyes of Examples 1 to 37 dye leather and paper in orange, brown, red brown, yellow brown or red shades with good fastness properties.

 1. A sulpho-free azo compound, in 1:1 metal complex or 1:2 metal complex form having on average at least 1.3 water-solubilising basic groups, of the formula II where c is 1 or 2; d' is 0 or 1; A1 and A3 form the group ―NH―Me―O― or ―O―Me―O― or ―NH―Me―NH― where Me is either a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 metal complex and a 1:2 metal complex; A2 is -OH or -NH2; D is a usual diazo component; W is a direct bond or Wa where Wa is in which the starred C-atom is attached to the N-atom of the group Z2 defined below and s is 1, 2, 3, 4, 5 or 6; X' is one of the groups X1 to X53 below: X1 is a direct bond, X2 a straight or branched chain alkylene group of (C1-4) carbon atoms, X3 -CO- X4 X5 ―S―, X6 ―O―, X7 ―CH=CH―, X8 ―S―S―, where R11 is halogen, (C1-4)alkyl or (C1-4)alkoxy R12 is hydrogen or (C1-4)alkyl; R13 is halogen, ―NH―CH2―CH2―OH or ―N(CH2―CH2OH)2; R14 is a straight or branched chain (C1-4)alkylene group and q is 1, 2, 3 or 4; a is 1 or 2; b is a number between 1 and 2; Rta'' is a group of αα or αβ where R2 is hydrogen, SO2―NH―(CH2)p―Z2, (C1-4)alkyl or (C1-4)alkoxy,
where p is 1, 2 or 3, R1 is C1-4alkyl, ―C2H4OH or (―CH2)p―N―(R1a)2 where R1a is propyl or butyl, R6 is C1-4alkyl, ―C2H4OH or (CH2)p―N―(R6')2 where R6' is (C1-4) alkyl and R6a is (C1-4)alkyl, ―C2H4OH, ―(CH2)p―N―(R6')2 or C2H4O―R6'; R3 is hydrogen (C1-4)alkyl, (C1-4)alkoxy, where R5 is hydrogen, (C1-4)alkyl or (C1-4)alkoxy; R5' is C1-4alkyl; no is a number between 1 and 2 inclusive and the group (―CH2―Z2) is attached to either of the phenyl groups J or K R7 is hydrogen, ―OH, (C1-4)alkyl, (C1-4)alkoxy ―NH―CO―NH2 or ―NH―CO―CH3; R8 is hydrogen, ―NH―CO―(CH2)p―Z2, or R4 is hydrogen, ―NO2, (C1-4)alkyl or (C1-4)alkoxy; K1 is a group of the formula R25 is (C1-4)alkya, ―COO―(R25a) or ―COOH where R25a is (C1-4)alkyl; R26 is hydrogen, halogen, (C1-4)alkyl or (C1-4)alkoxy; R124 is (C1-4)alkyl or ―(CH2)p―Z2; Ya is hydrogen, (C1-4)alkyl, ―C2H4OH or (CH2)p―Z2; Ya' is (C1-4)alkyl, preferably ―CH3; R9 is (C1-4)alkyl, or ―(CH2)p―Z2; R10 is hydrogen, (C1-4)alkyl, (C1-4)alkoxy, ―NH―CO ―CH3 or ―NH―CO―NH2; R124 is ―CH2)p―Z2, where R126 is hydrogen, ―OH, (C1-4)alkoxy, ―NH―CO―(CH2)p―Z2, ―CO―NH―(CH2)p―Z2, ―SO2―NH―(CH2)p―Z2, ―CH2)p―Z2 or and R128 is hydrogen or ―(CH2)p―Z2; Z2 is a group of the formula where each Ro independently is methyl, ethyl, β-hydroxyethyl, benzyl, provided that not more than one benzyl, is attached to a nitrogen atom, R127 is methyl or ethyl, m is 0, 1 or 2 and A⊖ is a non-chromophoric anion, with the provisos that i) each of the azo bridges in ring B is ortho to A1 or A2 above; ii) when c is 2, X' is attached to Rta'' when Rta'' is the group αα or to ring C; iii) when d' is 1 ring C can be additionally substituted by one or more of halogen, hydroxy, (C1-4)alkyl, (C1-4)alkoxy and ―NH―CO―NH2. 2. An azo compound according to Claim 1 of formula lid (in 1:1 metal complex form) or of the formula IIj (in 1:2 metal complex form) or of the formula Ilk (in 1:2 metal complex form) or of the formula III (in 1:2 metal complex form) or of the formula IIm (in 1:2 metal complex form) or where each R2a independently is hydrogen, ―NO2, ―SO2NH2, ―SO2―NH―CH3, ―SO2―N(CH3)2, ―SO2NH―C2H4OH, ―SO2―N(C2H4OH)2, ―SO2―N[C2H4―N(CH3)2]2 or ―SO2―NH―(CH2)3―Z2; each R3a, independently is hydrogen, ―NO2, ―SO2NH2, ―SO2―NH―CH3, ―SO2―N(CH3)2, ―SO2―NH―C2H4OH, ―SO2―N(C2H4OH)2, ―NH―CO―(CH2)p―Z2. ―CO―NH―(CH2)p―Z2, ―CH3, ―OCH3, ―SO2―NH―(CH2)p―Z2, in which R7a is hydrogen, ―OH, ―CH3, ―OCH3, ―NHCOCH3 or ―NHCONH2; R8a is hydrogen, ―NHCO―(CH2)pZ2 or no' is an average number between 1.0 and 1.7 K'1 is in which R9a is ―CH3 or C2H5, R10a is hydrogen, ―CH3, ―OCH3, ―NH―CO―CH3 or ―NH―CO―NH2; and R9' is hydrogen, ―CH3, ―C2H5, n-C3H7, n-C4H9, i-C3H7, i-C4H9, ―C2H4OH or ―(CH2)p―Z2; R4a is hydrogen, ―NO2, ―CH3 or ―OCH3; D1―Z2. or R15 is hydrogen, -OH, -OCH3, -CH3 or Cl, R16 is hydrogen or -CH3; qo is 2 to 5, preferably 2 or 3;
and all the other symbols are as defined above. Mea is copper, cobalt or chromium, R40 is hydrogen or Z2―D1―N=N―, Meg is cobalt, iron or chromium A1' is ―NH― or ―C―, R42 is ―(CH2)p―Z2, ―NH―(CH2)p―Z2 or R43 is ―CH3, C2H5 or (CH2)p―Z2; R44 is hydrogen, ―OH, (C1-4)alkoxy, ―NH―CO―(CH2)p―Z2, ―CO―NH―(CH2)p―Z2, ―SO2―NH―(CH2)p―Z2, or ―(CH2)p―Z2; R45 is hydrogen or ―(CH2)p―Z2; R2a' has the significances of R2a and may also be ―OH or ―NH2; and A2 is OH or NH2. 3. An azo compound according to Claim 1 of formula IIf in which is or where R2d is hydrogen, ―OH, ―CH3 or ―OCH3; and each ring C independently can be substituted in a position ortho to its azo bridge by -CH3 and/or ―OCH3 and the group Xa is in a meta- or para-position to the azo bridge of ring C and each azo bridge, in ring B is ortho to A; or A2 Xa is X1, X5, X6, X7, X10, X11' X12, X16' X17' X22, X25, X26, X27, X30, X31 X49 defined in Claim 1 or the following groups X2' ―CH2―, X2'' ―(CH2)2―, X2''' ―(CH2)3, Mea is copper, cobalt, iron or chromium where R11a is hydrogen, ―CI, ―CH3 or ―OCH3; R13a is ―CI, ―NH―CH2―CH2―OH or ―N(CH2―CH2―OH)2 and all the other symbols have been defined in Claim 2. 4. An azo compound according to Claim 3 of the formula IIg (in 1:1 metal complex form) in which Xb is X1, X11, X12, X17, X27, X48 defined in Claim 1; , defined in Claim 3; where ―D1―Z3 has the significances of ―D1―Z2 defined in Claim 2 except Z2 is replaced by Z3, A1' is -NH- or -0-, with the proviso that in ring C the group Xb is in a meta- or para-position to its azo bridge and Mea is defined in Claim 3. 5. An azo compound according to Claim 1 of the formula IIn in which R3c is hydrogen, ―NO2, ―CH3, ―OCH3, ―SO2―NH2, ―SO2NH(CH2)3N(CH3)2, ―SO2NHC2H4OH, ―NH―CO―(CH2)p―Z3, ―CH2―Z3, ―N=N-K'1, ―SO2NH(CH2)pN(CH3)2
and is hydrogen and,
where the group Z3―D1―N=N― has the significance then has the additional significance of R2b is hydrogen, NO2 or SO2NH2, no'' is 1.3 to 1.5, p is defined in Claim 1 and the other symbols are defined in Claim 3 and where the azo bridge is in ring B are ortho to the -0- or -OH group. 6. A sulpho-free azo compound, in metal-free form having on average at least 1.3 water-solubilising basic groups, of formula II' wherein A1 is -OH or -NH2; A3 is -OH or -NH2
and A2, R2, R3, X1, D, W, Z2, Rta'', a, b, c and d' have the meaning as defined in Claim 1. i) each of the azo bridges in ring B is ortho to A1 or A2 above; ii) when c is 2, X' is attached to Rta'' when Rta'' is the group αα or to ring C; iii) when d' is 1 ring C can be additionally substituted by one or more of halogen, hydroxy, (C1-4)alkyl, (C1-4)alkoxy and ―NH―CO―NH2. 7. An azo compound according to Claim 6 of formula Ila in which the symbols are as defined in Claim 2. 8. A method for dyeing a substrate comprising applying to that substrate a compound of formula II' as defined in Claim 1. 9. A process for the production of azo compounds of formula II' according to Claim 1, which comprises coupling a diazotised amine of formula γ with a coupling component of the formula 8 and where Ra is a group of formula la x is ―OH or NH2 and y is hydrogen, ―OH or ―NH2; x and y form the group -NH-Me-O-, -0-Me-0- or -NH-Me-NH- where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex; or capable of forming both a 1:1 and 1:2 metal complex n is 1 or 2; d is 0, 1 or 2; n' and da have the significances of n defined above and d' defined in Claim 1 with the proviso that n+n' is not greater than 2 and d and da is not greater than 2 Rt is Rta'' defined in Claim 1; R is a group of formula Ih where x, Ra, Rt and d' are defined above and x is x' where x' is as defined in Claim 1; and in the case of the metal complexes metallising with a metal capable of forming a 1:1 or a 1:2 metal complex or capable of forming both a 1:1 and 1:2 metal complex. 1. Sulfonsäuregruppenfreie Azoverbindungen in der 1 :1- oder 1:2-Metallkomplexstruktur, welche mindestens 1,3 wasserlöslich-machende basische Gruppen enthalten der Formel II worin c 1 oder 2, d' 0 oder 1, A1 und A3 eine Gruppe ―NH―Me―O― oder ―O―Me―O― oder ―NH―Me―NH― bilden, Me ein Metallatom das entweder einen 1:1- oder einen 1:2-Metallkomplex oder einen 1:1- und einen 1:2-Metallkomplex bilden kann, A2 -OH oder -NH2, D einen Rest einer üblichen Diazokomponente, W die direkte Bindung oder Wa, Wa ―(CH2)s― ―NHCO(CH2)s, ―CONH(CH2)3― oder ―SO2NH(CH2)s―, das mit * bezeichnete C-Atom an das N-Atom der Gruppe Z gebunden ist, das N-Atom der Gruppe Z gebunden ist, s 1, 2, 3, 4, 5 oder 6, X' eine Gruppe X1 bis X53, X1 die direkte Bindung, X2 eine geradkettige oder verzweigte Alkylengruppe mit 1-4C-Atomen, bedeuten,
worin R11 Halogen, (1―4C)-Alkyl oder (1―4C)-Alkoxy, R12 Wasserstoff oder (1―4C)-Alkyl, R13 Halogen, ―NHCH2CH2OH oder ―N(CH2CH2OH)2, R14 eine geradkettige oder verzweigte (1-4C)-Alkylen Gruppe, q 1, 2, 3 oder 4, a 1 oder 2, b eine Zahl zwischen 1 und 2, Rta" eine Gruppe oder R2 Wasserstoff, ―SO2NH(CH2)p―Z2, (1―4C)-Alkyl oder (1―4C)-Alkoxy, p 1, 2 oder 3, R1 (1―4C)-Alkyl, ―C2H4OH, ―(CH2)p―N(R1a)2, R1a Propyl oder Butyl, R6 (1―4C)-Alkyl, ―C2H4OH oder ―(CH2)p―N(R6')2, R6' (1―4C)-Alkyl, R6 (1―4C)-Alkyl, ―C2H4OH, ―(CH2)p―N(R6')2 oder C2H4O―R6', R3 Wasserstoff, (1-4C)-Alkyl, (1-4C)-Alkoxy, ―CONH(CH2)p―Z2, ―NHCO(CH2)p―Z2, ―SO2NH(CH2)p―Z2 oder ―CH2―Z2, Rs Wasserstoff, (1-4C)-Alkyl oder (1-4C)-Alkoxy, R5' (1―4C)-Alkyl, no eine Zahl zwischen 1 und 2 inklusiv, die Gruppe ―(CH2―Z2) entweder an die Phenylgruppe J oder K gebunden ist, R7 Wasserstoff, -OH, (1-4C)-Alkyl, (1-4C)-Alkoxy, -NHCONH2 oder -NHCOCH3, R8 Wasserstoff, ―NHCO(CH2)p―Z2 oder R4 Wasserstoff, NO2, (1―4C)-Alkyl oder (1―4C)-Alkoxy, K1 eine Gruppe der Formel R25 (1―4C)-Alkyl, ―COOR25a oder ―COOH, R25a (1―4C)-Alkyl, R26 Wasserstoff, Halogen, (1―4C)-Alkyl oder (1―4C)-Alkoxy, R124 (1―4C)-Alkyl oder ―(CH2)p―Z2, Ya Wasserstoff, (1―4C)-Alkyl, ―C2H4OH oder ―(CH2)p―Z2, Ya' (1―4C)-Alkyl, vorzugsweise ―CH3, Rg (1―4C)-Alkyl oder ―(CH2)p―Z2, R10 Wasserstoff, (1-4C)-Alkyl, (1-4C)-Alkoxy, -NHCOCH3 oder -NHCONH2, R125 ―(CH2)p―Z2, ―NH(CH2)p―Z2 oder R126 Wasserstoff, ―OH, (1―4C)-Alkoxy, ―NHCO(CH2)p―Z2, ―CONH(CH2)p―Z2, ―SO2NH(CH2)p―Z2, ―(CH2)p―Z2 oder R128 Wasserstoff oder ―(CH2)p―Z2, Z2 eine Gruppe der Formel jeder Rest Ro unabhängig voneinander Methyl oder Aethyl, β-Hydroxyäthyl, Benzyl, mit der Massgabe, dass nicht mehr als ein Benzyl, an ein N-Atom gebunden ist, R127 Methyl oder Aethyl, m 0, 1 oder 2 und A8 ein nicht-chromophores Anion bedeuten, mit der Massgabe, dass i) jede Azobrücke im Ring B ortho zu A1 oder A2 steht, ii) falls c für 2 steht, X' an Rta" gebunden ist, wenn Rta" eine der Gruppen αα) oder an den Ring C gebunden ist, . iii) falls d' für 1 steht, der Ring C zusätzlich durch Halogen, Hydroxy, (1-4C)-Alkyl, (1-4C)-Alkoxy oder -NHCONH2 substituiert sein kann. 2. Azoverbindung gemäss Anspruch 1 der Formel Ild) in der 1:1-Metallkomplexform oder der Formel IIj) in der 1:2-Metallkomplexform oder der Formel IIk) in der 1:2-Metallkomplexform oder der Formel III) in der 1:2-Metallkomplexform oder der Formel IIm) in der 1:2-Metallkomplexform oder R2a unabhängig voneinander Wasserstoff, ―NO2, ―SO2NH2, ―SO2―NH―CH3, ―SO2―N(CH3)2, ―SO2NH―C2H4OH, ―SO2―N(C2H4OH)2, ―SO2―N[C2H4―N(CH3)2]2 oder ―SO2―NH―(CH2)3―Z2; R3a unabhängig voneinder, ―NO2, ―SO2NHZ, ―SO2―NH―CH3, ―SO2―N(CH3)2, ―SO2―NH―C2H4OH, ―SO2―N(C2H4OH)2, ―NH―CO―(CH2)p―Z2, ―CO―NH―(CH2)p―Z2, ―CH3 ―OCH3, ―SO2―NH―(CH2)p―Z2, R7a Wasserstoff, ―OH, ―CH3, ―OCH3, ―NHCOCH3 oder ―NHCONH2; R8a Wasserstoff, ―NHCO―(CH2)p―Z2 oder no'a eine Zahl zwischen 1,0 und 1,7 K1' eine Gruppe der Formel R9a ―CH3 oder C2H5, R10a Wasserstoff, ―CH3, ―OCH3, ―NH―CO―CH3 oder ―NH―CO―NH2 und R9' Wasserstoff, ―CH3, ―C2H5, n-C3H7, n-C4H9, i-C3H7, i-C4H9, ―C2H4OH oder ―(CH2)p―Z2; R4a Wasserstoff, ―NO2, ―CH3 oder ―OCH3, ―D1―Z2 is oder R15 Wasserstoff ―OH, ―OCH3, ―CH3 oder Cl, R16 Wasserstoff oder ―CH3; qo 2 bis 5, vorteilhaft 2 oder 3; Mea Kupfer, Kobalt oder Chrom, R40 Wasserstoff oder Z2―D1―N=N―, Meg Kobalt, Eisen oder Chrom, A1' ―NH― oder ―C―, R42 ―(CH2)p―Z2, ―NH―(CH2)p―Z2 oder R43 ―CH3, C2H5 oder (CH2)p―Z2; R44 Wasserstoff, ―OH, (C1-4)-Alkoxy, ―NH―CO―(CH2)p―Z2, ―CO―NH―(CH2)p―Z2, ―SO2―NH―(CH2)p―Z2, oder ―(CH2)p―Z2; R45 Wasserstoff oder ―(CH2)p―Z2; R'2a eine der Bedeutungen von R2a oder ―OH oder ―NH2 und A2 OH oder NH2 bedeuten, 3. Azoverbindung gemäss Anspruch 1 der Formel IIf) worin oder worin R2d Wasserstoff, ―OH, ―CH3 oder ―OCH3 bedeutet, jeder der Ringe C unabhängig voneinander in ortho-Stellung zu den Azobrücken durch CH3 und/oder OCH3 substituiert sein kann und die Gruppe Xa in meta- oder para-Stellung zu der Azobrücke des Ringes C gebunden ist und jede Azobrücke im Ring B in ortho-Stellung zu A1' oder A2 gebunden ist, Xa steht für X1, X5, X6, X7, X10, X11, X12, X16, X17, X22, X25, X26, X27, X30, X31, X49 gemäss Anspruch 1 oder für die Gruppen X2'―CH2―, X2" ―(CH2)2―, X2''' ―(CH2)3―, Mea steht für Kupfer, Kobalt, Eisen oder Chrom, worin R11a Wasserstoff, ―CI, ―CH3 oder ―OCH3; R13a―CI, ―NH―CH2―CH2―OH oder ―N(CH2―CH2―OH)2 und worin die übrigen Symbole die in Anspruch 2 angegebenen Bedeutungen besitzen. 4. Azoverbindung gemäss Anspruch 3 der Formel IIg) in der 1:1-Metallkomplexform worin Xb X1, X11, X12, X17, X27' X49' gemäss Anspruch 1, gemäss Anspruch 3, bedeuten,
worin ―D1―Z3 eine der Bedeutungen von ―D1―Z2 gemäss Anspruch 2 besitzt, mit der Ausnahme, dass Z2 durch Z3 ersetzt ist, ―A1' für ―NH― oder ―O― steht, mit der Massgabe, das im Ring C die Gruppe Xb in meta- oder para-Stellung zur Azobrücke steht und Mea in Anspruch 3 definiert ist. 5. Azoverbindung gemäss Anspruch 1 der Formel Iln worin R3c Wasserstoff, ―NO2, ―CH3, ―OCH3, ―SO2―NH2, ―SO2NH(CH2)3N(CH3)2, ―SO2NHC2H4OH, ―NH―CO―(CH2)p―Z3, ―CH2―Z3, ―N=N―K'1, ―SO2NH(CH2)pN(CH3)2 und Wasserstoff bedeuten und falls die Gruppe Z3―D1―N=N― für einen Rest steht, dann die zusätzliche Bedeutung von hat, R2b Wasserstoff, N02 oder S02NH2, no" 1.3 bis 1.5 bedeutet und worin die Azobrücke im Ring B in ortho-Stellung zu -0- oder -OH steht. 6. Sulfonsäuregruppenfreie Azoverbindungen in der metallfreien Form, welche mindestens 1,3 wasserlöslich machende basische Gruppen enthalten der Formel worin A1 -OH oder -NH2 und A3 -OH oder -NH2 bedeuten, und die übrigen Symbole die im Anspruch 1 angagebenen Bedeutungen besitzen. 7. Azoverbindung gemäss Anspruch 6 der Formel IIa worin die Symbole die im Anspruch 2 angegebenen Bedeutungen besitzen. 8. Verfahren zum Färben von Substraten, dadurch gekennzeichnet, dass man hierzu eine Verbindung der Formel II' gemäss Anspruch 1 verwendet. 9. Verfahren zur Herstellung von Azoverbindungen der Formel II' gemäss Anspruch 1, dadurch gekennzeichnet, das man ein diazotiertes Amin der Formel γ) mit einer Kupplungskomponente der Formel worin Ra eine Gruppe der Formel x -OH oder -NH2 und y Wasserstoff, -OH oder -NH2 bedeuten, und worin x und y eine Gruppe -NH-Me-O-, -O-Me-O- oder -NH-Me-NH- bilden, worin Me ein Metallatom, das entweder einen 1:1- oder 1:2-Metallkomplex oder beides einen 1:1- und 1:2-Metallkomplex bilden kann, n 1 oder 2, d 0, 1 oder 2, n' und da eine der Bedeutungen von n haben und d' die im Anspruch 1 angegebene Bedeutung hat,
mit der Massgabe, dass n+n' nicht grösser als 2 und d und da nicht grösser als 2 ist,
worin Rt eine der Bedeutungen von Rta" hat, R eine Gruppe der Formel worin x, Ra, Rt und d' die zuvor genannten Bedeutungen besitzen und x für x' steht,
und im Falle der Metallkomplexform, die Verbindungen mit einem metallabgebenden Mittel das 1:1-oder 1:2-Metallkomplexe oder 1:1- und 1:2-Metallkomplexe bilden kann, metallisiert. 1. Un composé azoïque exempt de groupe sulfo, sous forme de complexe métallifère 1:1 ou de complexe métallifère 1:2 ayant en moyenne au moins 1,3 groupe basique hydrosolubilisant, de formule II' où c signifie 1 ou 2; d' signifie 0 ou 1; A1 et A3 forment le groupe -NH-Me-0- ou -0-Me-0- ou -NH-Me-NH- où Me est un métal capable de former soit un complexe métallifère 1:1, soit un complexe métallifère 1:2, ou bien capable de former un complexe métallifère 1:1 et un complexe métallifère 1:2, A2 est -OH ou -NH2; D est une composante de diazotation usuelle W est une*liaison directe ou bien Wa où est -(CH2)s-, -NHCO(CH2)s- -CONH-(CH2)s- ou -SO2-NH-(CH2)s-, dans lesquels l'atome de carbone marqué d'un astérisque est fixé à l'atome d'azote du groupe Z2 défini ci-après et s signifie 1, 2, 3, 4, 5 ou 6; X' est l'un des groupes X1 à X53 ci-dessous; X1 est une liaison directe, X2 un groupe alkylène à chaîne linéaire ou ramifié ayant de 1 à 4 atomes de carbone, X3 -CO- X1 est une liaison directe, X2 un groupe alkylène à chaîne linéaire ou ramifié ayant de 1 à 4 atomes de carbone, X3 -CO- X4 X5 -S-, X6 -O-, X7 -CH=CH-, X8 -S-S-, où R11 est un halogène, alkyle en C1-C4 ou alcoxy en C1-C4, R12 est l'hydrogène ou alkyle en C1-C4; R13 est un halogène, -NH-CH2-CH2-OH ou -N(CH2 CH2OH)2; R14 est un groupe alkylène en C1-C4 à chaîne linéaire ou ramifiée et q signifie 1, 2, 3 ou 4 a signifie 1 ou 2; b est un nombre entre 1 et 2; R"ta est un groupe aa ou α/β ou où R2 est l'hydrogène, SO2-NH-(CH2)p-Z2, alkyle en C1-C4 ou alcoxy en C1-C4, où p signifie 1, 2 ou 3, R1 est alkyle en C1-C4, -C2H40H ou (̵(CH2)p-N-(R1a)2 où R1a est propyle ou butyle, R6 est alkyle en C1-C4, -C2H40H ou (CH2)p-N-(R6')2 où R6' est alkyle en C1-C4 et R6a est alkyle en C1-C4, -C2H4OH, -(CH2)p-N-(R6')2 ou C2H4O-R6'; R3 est l'hydrogène, alkyle en C1-C4, alcoxy en C1-C4, -CO-NH-(CH2)p-Z2, -NH-CO-(CH2)p-N-Z2, -SO2-NH-(CH2)p-Z2 ou CH2-Z2, où R5 est l'hydrogène, alkyle en C1-C4 ou alcoxy en C1-C4; R5' est alkyle en C1-C4; no est un nombre entre 1 et 2 inclus et le groupe (̵CH2-Z2) est fixé à l'un quelconque des groupes phényle J ou K R7 est l'hydrogène, -OH, alkyle en C1-C4, alcoxy en C1-C4, -NH-CO-NH2 ou -NH-CO-CH3; R8 est l'hydrogène, -NH-CO-(CH2)p-Z2, ou R4 est l'hydrogène, -NO2, alkyle en C1-C4 ou alcoxy en C1-C4; K1 est un groupe de formule R124 -CO-CH-CO-R125; R25 est alkyle en C1-C4, -COO-(R25a) ou -COOH où R25a est alkyle en C1-C4; R26 est l'hydrogène, un halogène, alkyle en C1-C4 ou alcoxy en C1-C4; R124 est alkyle en C1-C4 ou -(CH2)p-Z2; Ya est l'hydrogène, alkyle en C1-C4, -C2H40H ou (CH2)p-Z2; Ya' est alkyle en C1-C4, de préférence -CH3; R9 est alkyle en C1-C4 ou -(CH2)p-Z2; R10 est l'hydrogène, alkyle en C1-C4, alcoxy en C1-C4, -NH-CO-CH3 ou -NH-CO-NH2; R125 est -(CH2)p-Z2, où R128 est l'hydrogène, -OH, alcoxy en C1-C4, -NH-CO-(CH2)p-Z2, -CO-NH-(CH2)p-Z2, -SO2-NH-(CH2)p-Z2, -(CH2)p-Z2 ou et R128 est l'hydrogène ou -(CH2)p-Z2; Z2 est un groupe de formule où chaque Ro indépendamment est méthyle, éthyle, β-hydroxyéthyle, benzyle, à condition que pas plus d'un benzyle, soit fixé à l'atome d'azote, R127 est méthyle ou éthyle, m signifie 0, 1 ou 2 et A⊖ est an anion non chromophore, avec les conditions que i) chacun des ponts azo dans le cycle B soit en ortho de A1 ou A2 ci-dessus, ii) lorsque c signifie 2, X' soit fixé à Rta" lorsque Rta' est le groupe aa ou au cycle C; iii) lorsque d'signifie 1 le cycle C puisse être substitué en plus par un ou plusieurs halogènes, hydroxy, alkyle en C1-C4, alcoxy en C1-C4 et -NH-CO-NH2. 2. Un composé azoïque selon la revendication 1 de formule Ild (sous forme de complexe métallifère 1:1) ou de formule Ilj (sous forme de complexe métallifère 1:2) ou de formule Ilk (sous forme de complexe métallifère 1:2) ou de formule III (sous forme de complexe métallifère 1:2) ou de formule Ilm (sous forme de complexe métallifère 1:2) dans lesquelles est ou ou chaque R2a indépendamment est l'hydrogène, -N02, -SO2NH2, -SO2-NH-CH3, -SO2-N(CH3)2, -SO2NH-C2H4OH, -SO2-N(C2H,OH)2, -SO2-N[C2H4-N(CH3)2]2 ou -SO2-NH (CH2)3 Z2% chaque R3a, indépendamment, est l'hydrogène, -NO2, -SO2NH2, -SO2-NH-CH3, -SO2-N(CH3)2, -SO2-NH-C2H4oH, -SO2-N(C2H4OH)2, -NH-CO-(CH2)p-Z2, -CO-NH-(CH2)p-Z2, -CH3, -OCH3, -SO2-NH-(CH2)p-Z2, dans lesquelles R7a est l'hydrogène, -OH, -CH3, -OCH3, -NHCOCH3 ou -NHCONH2; R8a est l'hydrogène -NHCO-(CH2)p-Z2 ou est un nombre moyen entre 1,0 et 1,7 est dans lesquelles R9a est -CH3 ou C2H5, R10a est l'hydrogène, -CH3, -OCH3, -NH-CO-CH3 ou -NH-CO-NH2; et est l'hydrogène, -CH3, -C2H5, n-C3-H7, n-C4H9, i-C3-H7, i-C4H9, -C2H4OH ou -(CH2)p-Z2; R4a est l'hydrogène, -N02, -CH3 ou -OCH3; D1-Z2 ou R15 est l'hydrogène, -OH, -OCH3, -CH3 ou CI, R16 est l'hydrogène ou -CH3; qo signifie 2 à 5 de préférence 2 ou 3; et tous les autres symboles sont comme définis ci-dessus. Mea est le cuivre, le cobalt ou le chrome, R40 est l'hydrogène ou Z2-D1-N=N-, Meg est le cobalt, le fer ou le chrome A; est -NH- ou -0-, R42 est -(CH2)p-Z2, -NH-(CH2)p-Z2 ou R43 est -CH3, C2H5 ou (CH2)p-Z2; R44 est l'hydrogène, -OH, alcoxy en C1-C4, -NH-CO-(CH2)P-Z2, -CO-NH-(CH2)p-Z2, -SO2-NH-(CH2)p-Z2, ou -(CH2)p-Z2; R45 est l'hydrogène ou -(CH2)p-Z2; a les significations de R2a et peut aussi être -OH ou -NH2 et; A2 est OH ou NH2. 3. Un composé azoïque selon la revendication 1 de formule Ilf dans laquelle est ou où R2d est l'hydrogène, -OH, -CH3 ou -OCH3;
et chaque cycle C indépendamment peut être substitué en position ortho de son pont azo par -CH3 et/ou -OCH3 et le groupe Xa est en position méta ou para du pont azo du cycle C et chaque pont azo, dans le cycle B est en ortho de A1 ou A2 Xa est X1, X5, X6, X7, X10, X11, X12, X16, X17, X22, X25, X26, X27, X30, X31 X49 définis à la revendication 1 ou les groupes suivants -CH2-, -(CH2)2-, X'''2 -(CH2)3 Mea est le cuivre, le cobalt, le fer ou le chrome où R11a est l'hydrogène, -CI, -CH3 ou -OCH3; R13a est -CI, -NH-CH2-CH2-OH ou -N(CH2-CH2-OH)2 et tous les autres symboles ont été définis à la revendication 2. 4. Un composé azoïque selon la revendication 3 de formule Ilg (sous forme de complexe métallifère 1:1) dans laquelle Xb est X1, X11, X12, X17, X27, X49' définis la revendication 1; définis à la revendication 3; où -D1-Z3 a les significations de -D1-Z2 défini à la revendication 2 excepté que Z2 est remplacé par Z3, est -NH- ou -0-, avec la condition que dans le cycle C le groupe Xb soit en position méta ou para de son pont azo et Mea est défini à la revendication 3. 5. Un composé azoïque selon la revendication 1 de formule Iln dans laquelle R3c est l'hydrogène, -N02, -CH3, -OCH3, -SO2-NH2, -SO2NH(CH2)3N(CH3)2, -So2NHC2H4OH, -NH-CO-(CH2)p-Z3, -CH2-Z3, -N=N-K1', -SO2NH(CH2)pN(CH3)2 et Rt est l'hydrogène et,
quand le groupe Z3-D1-N=N- a la signification alors a la signification supplémentaire de R2b est l'hydrogène, NO2 ou SO2NH2, no'' signifie 1,3 à 1,5. p est défini à la revendication 1 et les autres symboles sont définis à la revendication 3 et où le pont azo est, dans le cycle B en ortho du groupe -0- ou -OH. 6. Un compose azoïque exempt de groupe sulfo, sous forme non métallisée ayant en moyenne au moins 1,3 groupe basique hydrosolubilisant, de formule II' dans laquelle A1 est -OH ou -NH2; A3 est -OH ou -NH2 et A2, R2, R3, X', D, W, Z2, R''ta, a, b, c et d' ont la signification comme définie à la revendication 1 avec la condition que i) chacun des ponts azo dans le cycle B soit en ortho de A, ou A2 ci-dessus; ii) lorsque c signifie 2, X' soit fixé à R''ta lorsque Rta'' est le groupe aa ou au cycle C; iii) lorsque d'signifie 1 le cycle C puisse être substitué en plus par un ou plusieurs halogènes, hydroxy, alkyle en C1-C4, alcoxy en C1-C4 et -NH-CO-NH2. 7. Un composé azoïque selon la revendication 6 de formule IIa t dans laquelle les symboles sont comme définis à la revendication 2. 8. Une méthode pour la teinture d'un substrat comprenant l'application sur ce substrat d'un composé de formule II' comme défini à la revendication 1. 9. Un procédé pour la production de composés azoïques de formule II' selon la revendication 1, qui comprend la copulation d'une amine diazotée de formule y avec une composante de copulation de formule et où Ra est un groupe de formule la x est -OH ou NH2 et y est l'hydrogène, -OH ou -NH2; x et y forment le groupe -NH-Me-O-, -O-Me-O- ou -NH-Me-NH- où Me est un métal capable de former soit un complexe métallifère 1:1, soit un complexe métallifère 1:2; ou bien capable de former un complexe métallifère 1:1 et un complexe métallifère 1:2 n signifie 1 ou 2; d signifie 0, 1 ou 2; n' et da ont les significations de n défini ci-dessus et de d' défini à la revendication 1 avec la condition que n+n' ne soit pas supérieur à 2 et que d et da ne soit pas supérieur à 2 Rt est Rta'' défini à la revendication 1; R est un groupe de formule Ih où x, Ra, Rt et d' sont définis ci-dessus et x est x' où x' est comme défini à la revendication 1; et dans le cas des complexes métallifères la métallisation avec un métal capable de former un complexe métallifère 1:1 ou 1:2 ou capable de former un complexe métallifère 1:1 et un complexe métallifère 1:2.